CN103121922A - Methods and apparatus for producing alcohols from syngas - Google Patents

Methods and apparatus for producing alcohols from syngas Download PDF

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Publication number
CN103121922A
CN103121922A CN2012104742355A CN201210474235A CN103121922A CN 103121922 A CN103121922 A CN 103121922A CN 2012104742355 A CN2012104742355 A CN 2012104742355A CN 201210474235 A CN201210474235 A CN 201210474235A CN 103121922 A CN103121922 A CN 103121922A
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alcohol
ethanol
synthetic gas
purifying
reactor
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Inventor
罗伯特·E·克莱珀
阿里·葛尔特塞玛
海因茨·尤尔根·罗伯塔
罗纳德·C·斯蒂茨
理查德·里德利
沙基尔·H·特米兹
弗朗西斯·M·费拉罗
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Albemarle Corp
Range Fuels Inc
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Albemarle Corp
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Priority claimed from US12/166,203 external-priority patent/US20090018371A1/en
Priority claimed from US12/166,212 external-priority patent/US9227895B2/en
Application filed by Albemarle Corp filed Critical Albemarle Corp
Publication of CN103121922A publication Critical patent/CN103121922A/en
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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Abstract

Methods and apparatus for producing alcohols from syngas are disclosed herein. In some variations, syngas is catalytically converted to methanol in a first reaction zone, and residual syngas from the first reaction zone is then catalytically converted to ethanol in a second reaction zone. Also, in some variations, syngas is catalytically converted to methanol in high yield in a first reaction zone, and the methanol is then converted (optionally, with additional syngas) to ethanol in a second reaction zone.

Description

Be used for being produced by synthetic gas the method and apparatus of alcohol
The application is to be on July 2nd, 2008, denomination of invention the applying date be the dividing an application of the application for a patent for invention of the PCT/US2008/069071 of " being used for being produced by synthetic gas the method and apparatus of alcohol ", the Chinese patent application of original application number is 200880024056.3.
The right of priority data
It is all the benefit of priority of No. the 60/948th, 650, the U.S. Provisional Patent Application submitted on July 9th, 2007 and the 60/948th, No. 657 that this international patent application requires; And also requiring is all the benefit of priority of No. the 12/166th, 203, the non-temporary patent application of the U.S. submitted on July 1st, 2008 and the 12/166th, No. 212, and whole disclosures of above-mentioned patent application are incorporated this paper into accordingly by reference for all purposes.
Technical field
The present invention relates generally to for will be converted into such as the carbon raw material of cellulose biomass the method for synthetic gas, and also relate to for the method that synthetic gas is converted into such as the product of alcohol (as, ethanol).
Background technology
Ethanol can replace petroleum-based products such as gasoline as fuel and fuel dope with the alcohol mixture that comprises ethanol.This purposes of alcohol can reduce the demand of Imported oil.In addition, when alcohol is during by the raw material production except fossil oil, it can be eco-friendly especially that alcohol replaces petroleum based fuels and fuel dope.
A kind of route of synthesis of alcohol is by being used for synthetic gas is converted into the catalysis process of alcohol.Synthetic gas (syngas) (or synthetic gas (synthesis gas)) is monoxide (CO) and hydrogen (H 2) mixture.Usually, synthetic gas can be by any carbonaceous material production.Particularly, can be synthetic gas with the Wood Adhesives from Biomass such as agricultural waste, Forest products, grass and other cellulose materialss.
Having multiple transformation technology is synthetic gas with these feedstock conversion.Method for transformation can utilize the combination of one or more steps of the gasification, pyrolysis, steam reformation and/or the partial oxidation that comprise carbonaceous material.
Since nineteen twenties, to know, methyl alcohol and other pure mixtures can obtain by synthetic gas is reacted people such as (, Cat.Rev.-Sci.andEng.33 (1-2), 109-168,1991) Forzatti on some catalyzer.Fischcr and Tropsch observe the hydrocarbon synthesis catalyst generation as the straight chain alcohol (Fischer and Tropsch, Brennst.-Chem.7:97,1926) of by product about identical period greatly.
Yet, current Innovative method and the device that synthetic gas need to be converted into such as the alcohol of ethanol.
Summary of the invention
In some embodiments, the invention provides a kind of one or more C of production 2-C 4The method of alcohol, described method comprises:
(i) synthetic gas is incorporated in the first reaction zone that comprises at least the first catalyzer;
(ii) with the first catalyzer, the part of synthetic gas is converted into methyl alcohol;
(iii) will be incorporated in the second reaction zone that comprises at least the second catalyzer from synthetic gas and the methyl alcohol of the first reaction zone; And
At least a portion that (iv) will be introduced in synthetic gas in second reaction zone and methyl alcohol with the second catalyzer transforms, and comprises one or more C with generation 2-C 4The product stream of alcohol, described C 2-C 4Alcohol is ethanol, 1-propyl alcohol or n-butyl alcohol for example.
Second reaction zone can be in the reactor identical from the first reaction zone or in the reactor different with the first reaction zone.
In some embodiments, the synthetic gas that is introduced in the first reaction zone has initial H 2/ CO ratio is converted into synthetic gas methyl alcohol and makes the synthetic gas in being introduced in second reaction zone have the 2nd H in the first reaction zone 2/ CO ratio, and with by described initial H 2The yield that/CO ratio provides is compared, described the 2nd H 2One or more C that/CO ratio provides in described second reaction zone 2-C 4The yield of alcohol increases.The 2nd H 2/ CO ratio is preferably lower than initial H 2/ CO ratio.
In some embodiments, described method also comprises and other methyl alcohol is incorporated in second reaction zone and is converted into one or more C with at least a portion that the second catalyzer will be introduced in the other methyl alcohol in second reaction zone 2-C 4Alcohol.In certain embodiments, at least a portion that is introduced in the other methyl alcohol in second reaction zone reclaims from product stream in advance.In certain methods, other synthetic gas (not being the unreacted synthetic gas from the first reaction zone) is incorporated in second reaction zone, and at least a portion that then will be introduced in the other synthetic gas in second reaction zone with the second catalyzer is converted into one or more C 2-C 4Alcohol.Can reclaim synthetic gas and this synthetic gas is cycled through at least one reaction zone from product stream.
The first catalyzer can comprise the material of the group that the freely following material of choosing forms: ZnO/Cr 2O 3, Cu/ZnO, Cu/ZnO/Al 2O 3, Cu/ZnO/Cr 2O 3, Cu/ThO 2, Co/S, Mo/S, Co/Mo/S, Ni/S, Ni/Mo/S, Ni/Co/Mo/S and with the aforementioned substances of Mn and/or V combination in any.The first catalyzer preferably includes alkaline promoter.
The second catalyzer can comprise the material of the group that the freely following material of choosing forms: ZnO/Cr 2O 3, Cu/ZnO, Cu/ZnO/Al 2O 3, CuO/CoO, CuO/CoO/Al 2O 3, Co/S, Mo/S, Co/Mo/S, Rh/Ti/SiO 2, Rh/Mn/SiO 2, Rh/Ti/Fe/Ir/SiO 2, Rh/Mn/MCM-41, Ni/S, Ni/Mo/S, Ni/Co/Mo/S and with the aforementioned substances of Mn and/or V combination in any.The second catalyzer preferably includes alkaline promoter.In some embodiments, the first catalyzer and the second catalyzer can have substantially the same initial composition.
In some embodiments, the invention provides a kind of one or more C of production 2-C 4The method of alcohol, described method comprises:
(i) synthetic gas with the first amount is incorporated in the first reaction zone that comprises the first catalyzer at least;
(ii) with the first catalyzer, at least a portion of synthetic gas of the first amount is converted into methyl alcohol;
(iii) methyl alcohol is incorporated in the second reaction zone that comprises at least the second catalyzer;
(iv) synthetic gas with the second amount is incorporated in second reaction zone; And
(v) make at least a portion reaction of the synthetic gas of at least a portion of being introduced in the methyl alcohol in second reaction zone and the second amount with the second catalyzer, comprise one or more C with production 2-C 4The product stream of alcohol.
The synthetic gas of the second amount can be included in responseless synthetic gas in the first reaction zone.The synthetic gas of the second amount can comprise the synthetic gas that separates and reclaim from product stream in addition.And the synthetic gas of the second amount can comprise the other synthetic gas that is not introduced in the first reaction zone.In some embodiments, the synthetic gas of the second amount comprises the synthetic gas that is produced by the methyl alcohol in the first reaction zone.
In some embodiments, the first reaction zone is in the first reactor, second reaction zone is in the second reactor, and the output stream of the first reactor comprises from the first reaction zone and is incorporated into synthetic gas second reaction zone, and described method also comprises at least a portion of isolating the methyl alcohol of producing in the first reaction zone from output stream.The first reaction zone and second reaction zone can be all in single reaction vessels.
In certain embodiments, can be with other or CO that reclaim 2Be incorporated in the first reaction zone, wherein make CO 2At least a portion and the H of existence 2Reaction is to produce CO 2Derivative methyl alcohol.In second reaction zone, can be with CO 2Derivative methyl alcohol is converted into one or more C at least in part 2-C 4Alcohol (as, ethanol).
Usually, the invention describes a kind of production for generation of the method for the intermediate lower alcohol of higher alcohols.C n+m(n+m=2-10) at first alcohol can produce C according to following steps n(n=1-5) alcohol is produced:
(i) synthetic gas is incorporated in the first reaction zone that comprises at least the first catalyzer;
(ii) with the first catalyzer, the part of synthetic gas is converted into C nAlcohol;
(iii) will be from synthetic gas and the C of the first reaction zone nAlcohol is incorporated in the second reaction zone that comprises the second catalyzer at least; And
(iv) will be introduced in synthetic gas and C in second reaction zone with the second catalyzer nAt least a portion of alcohol transforms, and comprises C with production n+mThe product stream of alcohol.
In some embodiments, the intermediate production of higher alcohols can be for the production of the lower alcohol as final product.Particularly, method can comprise with the second catalyzer and will be introduced in synthetic gas and C in second reaction zone nAt least a portion of alcohol transforms to produce to comprise and compares C nThe product stream of the alcohol of few at least one carbon number of alcohol, wherein n is selected from 2 to 5.
Description of drawings
Fig. 1 has shown according to version and uses two reactors of series connection by the technical process of synthetic gas methanol and ethanol.
Fig. 2 has shown according to version and uses two reaction zones of connecting in single reaction vessel by the technical process of synthetic gas methanol and ethanol.
Fig. 3 shown according to version and uses two reactors of series connection by the technical process of synthetic gas methanol and ethanol, and some or all of the methyl alcohol of producing in the first reactor shift from the second reactor.
Fig. 4 has shown according to another version and uses two reactors of series connection by the technical process of synthetic gas methanol and ethanol.
Fig. 5 shown according to version and uses two reactors of series connection by the technical process of synthetic gas methanol and ethanol, and the first reactor with high produced in yields methyl alcohol in order to be converted into ethanol in the second reactor.
When below the initial simple accompanying drawing reference of describing of those skilled in the art's combination, more detailed the present invention describes, these and other embodiments of the present invention, Characteristics and advantages will become more obvious.
Embodiment
Now will be can realize desired invention so that those of ordinary skill in the art can make and use mode of the present invention to come further to describe in more detail certain embodiments of the present invention.
As what use in this specification sheets and appended claim, singulative " (a) ", " one (an) " and " should (the) " comprise plural indicator, unless context is clearly pointed out in addition.Unless otherwise defined, all technical terms used herein and scientific terminology have the identical implication that those skilled in the art understand usually.
Unless otherwise noted, all numerals of the expression response condition of using in specification sheets and claim, stoichiometry, concentration of component etc. will be understood to be modified by term " about " in all cases.Therefore, unless point out on the contrary, the digital parameters that proposes in specification sheets below and appended claim is the approximation that can change according to concrete analytical technology at least.Any numerical value comprises inevitable some error that is caused by the standard deviation that exists in its corresponding thermometrically result inherently.
As used herein, " C 1-C 4Alcohol " mean to be selected from one or more alcohol of methyl alcohol, ethanol, propyl alcohol and butanols, comprise all known isomer of these compounds.Although some embodiments are described about the highly selective to ethanol, the present invention can also implement to provide to the highly selective of methyl alcohol, propyl alcohol and/or butanols or to the mode of optionally some combination of methyl alcohol, ethanol, propyl alcohol and butanols." C 2-C 4Alcohol " mean to be selected from one or more alcohol of ethanol, propyl alcohol and butanols, comprise all known isomer of these compounds.
Herein disclosed is for producing C by synthetic gas 1-C 4The method and apparatus of alcohol.In some versions of these method and apparatus, synthetic gas is catalytically conveted to methyl alcohol in the first reaction zone, and then is catalytically conveted to ethanol from the residual synthetic gas of the first reaction zone in second reaction zone.With reference to figure 1, for example, in a version, synthetic gas incoming flow 100 is incorporated in the first reactor 105 that comprises the first reaction zone 110.One or more catalyzer in reaction zone 110 are converted into methyl alcohol with at least a portion of synthetic gas incoming flow 100, at least a portion of comprising from residual (unreacted) synthetic gas of incoming flow 100, methyl alcohol to be provided and in some versions, to comprise the intermediate product stream 115 of higher alcohols and/or other reaction product.
At least a portion of intermediate product stream 115 is incorporated in the second reactor 120 that comprises second reaction zone 125.One or more catalyzer in reaction zone 125 will transform from least a portion of the synthetic gas of intermediate product stream 115 and/or from least a portion of the methyl alcohol of intermediate product stream 115, comprise ethanol and in some versions to provide, comprise methyl alcohol, higher alcohols, other reaction product and/or from the product stream 130 of the unreacted synthetic gas of intermediate product stream 115.
The various components of product stream 130 for example methyl alcohol, ethanol, alcohol mixture (as, methyl alcohol, ethanol and/or higher alcohols), water and unreacted synthetic gas can open by method described herein or by ordinary method is separated, and (randomly) is purified.These methods for example can comprise, distillation and membrane separating method and dry or use molecular sieve purification.
Synthetic gas incoming flow 100 can be produced by any suitable raw material in any suitable mode known to persons of ordinary skill in the art.In some versions, in being introduced in reactor 105 before, synthetic gas incoming flow 100 is filtered, purifying or otherwise regulate.For example, the compound of carbonic acid gas, benzene, toluene, ethylbenzene, dimethylbenzene, sulphur, metal and/or other impurity or potential catalyzer poison can be removed from synthetic gas incoming flow 100 by ordinary method known to persons of ordinary skill in the art.
In some versions, synthetic gas incoming flow 100 comprises H 2/ CO ratio has approximately 0.5 to approximately 3.0, and approximately 1.0 to approximately 1.5 or approximately 1.5 to the about H of the value between 2.0 2And CO.In some versions, the H in incoming flow 100 2/ CO ratio can affect the yield of methyl alcohol in reactor 105 and other products.Preferred H in these versions 2/ CO ratio can depend on one or more catalyzer that use in reactor 105 and depend on operational condition.Therefore, in some versions, the production of synthetic gas incoming flow 100 and/or adjusting subsequently (conditioning) are controlled as produces the H have in the required scope of the production of optimizing for example methyl alcohol, ethanol or methyl alcohol and ethanol 2The synthetic gas of/CO ratio.
Synthetic gas incoming flow 100 can randomly be pressurizeed and/or heat by compressor and well heater (not shown) before enter reactor 105.In some versions, synthetic gas incoming flow 100 with approximately 300 °F to approximately 600 °F temperature and approximately 500psig enter reactor 105 to the about pressure of 2500psig.In some embodiments, temperature is at approximately 300 °F to approximately 400 °F, approximately 400 °F to approximately 500 °F or approximately 500 °F to approximately between 600 °F.In some embodiments, pressure at about 500psig to about 1000psig, approximately 1000psig to about 2000psig or approximately 2000psig to approximately between 2500psig.
Reactor 105 can be suitable for synthetic gas be converted into methyl alcohol, comprise methyl alcohol, the catalyticreactor of any type of the alcohol mixture of higher alcohols and/or other products.Reactor 105 can be any suitable fixed-bed reactor for example.In some versions, reactor 105 comprises the pipe that is filled with one or more catalyzer.Synthetic gas by pipe experiences catalyzed reaction to form methyl alcohol and in some versions, to form higher alcohols or other products.In some embodiments, catalysis occurs in pelletizing (pellet) or in homogeneous phase.
Reactor 105 can be for example approximately 400 °F to approximately 700 °F temperature and approximately 500psig operate under the pressure of about 2500psig.In some embodiments, temperature is at approximately 400 °F to approximately 500 °F, approximately 500 °F to approximately 600 °F or approximately 600 °F to approximately between 700 °F.In some embodiments, pressure at about 500psig to about 1000psig, approximately 1000psig to about 2000psig or approximately 2000psig to about 2500psig.
In some embodiments, effectively be used for comprising approximately 0.1-10 second by the condition of synthetic gas production alcohol, preferably about average reactor residence time of 0.5-2 second." the average reactor residence time " is the mean value that distributes the residence time of reactor content under the operational condition of reality.Catalyzer can also be calculated by the technician duration of contact, and these times will be also usually in the 0.1-10 scope of second, but should be understood that certainly and can operate within the shorter or long time.
Being used for that synthetic gas is converted into pure reactor can be designed and operate in various modes.Reactor operation can be continuous, semi-continuous or in batches.Preferred continuous and operation that be in stable state basically.Flow pattern can be basically plug flow, the well-mixed or flow pattern between these egregious cases basically.The flow direction can be vertically upward, vertically downward or level.Vertical configuration can be preferred.
" reactor " can be in fact to be a series of some reactors of various layouts or the network of some reactors.For example, in some versions, reactor comprises a large amount of pipes that is filled with one or more catalyzer.
Any suitable catalyzer or the combination of catalyzer can be used in reactor 105, so that the reaction that catalysis is converted into synthetic gas methyl alcohol and randomly is converted into higher alcohols and/or other products.Suitable catalyzer can include but not limited to, one or more in following material: ZnO/Cr 2O 3, Cu/ZnO, Cu/ZnO/Al 2O 3, Cu/ZnO/Cr 2O 3, Cu/ThO 2, Co/Mo/S, Co/S, Mo/S, Ni/S, Ni/Mo/S, Ni/Co/Mo/S, Rh, Ti, Fe, Ir and with the aforementioned substances of Mn and/or V combination in any.Add alkaline promoter (as, K, Li, Na, Rb, Cs and Fr) increased some activity and selectivities to alcohol in these catalyzer.Alkaline promoter comprises alkaline-earth metal and rare earth metal.In some embodiments, nonmetallic alkali also can be used as effective promotor.
Catalyzer can be packed bed or fluidized-bed mutually.Granules of catalyst can be made and be shaped according to size, and making in some embodiments, chemical property is subjected to mass transfer limited or is subjected to kinetic control.Catalyzer can be the form of powder, ball, particle, pearl, extrudate etc.When support of the catalyst was randomly adopted, carrier can present any profile, such as ball, ball, monolithic channel etc.Carrier can with the active metal substance coprecipitation; Perhaps carrier can with the catalytic metal mass treatment and then former state use or form aforementioned shapes; Perhaps carrier can form aforementioned shapes and then process with catalytic specie.
In some versions, be converted into methyl alcohol up to about 50% CO in reaction zone 110 in synthetic gas incoming flow 100.In some versions, can comprise approximately 5% to about 50% methyl alcohol, approximately 5% to about 50% ethanol, approximately 5% to about 25% CO, approximately 5% to about 25% H from the intermediate product stream 115 of reactor 105 output 2With approximately 2% to about 35% CO 2And other gases.In some embodiments, intermediate product stream 115 also comprises one or more higher alcoholss, for example ethanol, propyl alcohol or butanols.
In some versions, the H in intermediate product stream 115 2/ CO ratio can affect the yield of ethanol in reactor 120 and other products.Preferred H in these versions 2/ CO ratio can depend on one or more catalyzer that use in reactor 120 and depend on operational condition.H in intermediate product stream 115 2/ CO ratio can be different from the H of incoming flow 100 2/ CO ratio, this is the reaction that occurs due in reactor 105.In some versions, the H in intermediate product stream 115 2/ CO ratio provides the H than incoming flow 100 in reactor 120 2The ethanol yield that the ethanol yield that/CO ratio provides is high.In these versions, the viewpoint of the ethanol yield from reactor 120, operant response device 105 comes methanol for example to improve the H that is fed into the synthetic gas in reactor 120 2/ CO ratio.
In an example, incoming flow 100 comprises and has approximately 1.5 to about 2 H 2The synthetic gas of/CO ratio, and for produce the preferred H of ethanol at reactor 120 2/ CO ratio is approximately 1.Operant response device 105 H in the synthetic gas that come the production methanol consumption in this example 2, so that with the H in intermediate product stream 115 2/ CO ratio is reduced to the value close to 1, and has therefore improved the ethanol yield in reactor 120.In certain embodiments, the catalyzer in reactor 105 is the Cu/ZnO/ aluminium oxide catalyst.
Reactor 120 can be to be suitable for synthetic gas, methyl alcohol and/or synthetic gas are added that methanol conversion is ethanol and the catalyticreactor that randomly is converted into any type of higher alcohols and/or other products.For example, reactor 120 can be any suitable fixed-bed reactor.In some versions, reactor 120 comprises the pipe that is filled with one or more catalyzer.Synthetic gas and/or methyl alcohol by pipe experience surface-catalyzed reactions to form ethanol and in some versions, to form higher alcohols and/or other products.
Although do not expect to be subject to any specific theoretical constraint, but think at present, methyl alcohol can be converted into synthetic gas and therefore be converted into ethanol, and methyl alcohol can be converted into ethanol via homologation, and/or methyl alcohol can be converted into ethanol by other mechanism.
Reactor 120 can be for example approximately 500 °F to approximately 800 °F temperature and approximately 500psig operate under the pressure of about 2500psig.In some embodiments, temperature is at approximately 500 °F to approximately 600 °F, approximately 600 °F to approximately 700 °F or approximately 700 °F to approximately between 800 °F.In some embodiments, pressure be approximately 500psig to about 1000psig, approximately 1000psig to about 2000psig or approximately 2000psig to about 2500psig.
Any suitable catalyzer or the combination of catalyzer can be used in reactor 120, so that catalysis is ethanol and the reaction that randomly is converted into higher alcohols and/or other products with synthetic gas, methyl alcohol and/or synthetic gas+methanol conversion.Suitable catalyzer can include but not limited to, basic metal/ZnO/Cr 2O 3, Cu/ZnO, Cu/ZnO/Al 2O 3, CuO/CoO, CuO/CoO/Al 2O 3, Mo/S, Co/Mo/S, Ni/S, Ni/Mo/S, Ni/Co/Mo/S, Rh/Ti/SiO 2, Rh/Mn/SiO 2, Rh/Ti/Fe/Ir/SiO 2, Rh/Mn/MCM-41, Cu, Zn, Rh, Ti, Fe, Ir and composition thereof.Add alkaline promoter (as, K, Li, Na, Rb, Cs and Fr) increased some in these catalyzer to ethanol or other C 2+The activity and selectivity of alcohol.Alkaline promoter comprises alkaline-earth metal and rare earth metal.In some embodiments, nonmetallic alkali also can be used as effective promotor.
In some embodiments, the catalyzer that is used for reactor 120 can comprise one or more of following material: ZnO/Cr 2O 3, Cu/ZnO, Cu/ZnO/Al 2O 3, CuO/CoO, CuO/CoO/Al 2O 3, Co/S, Mo/S, Co/Mo/S, Rh/Ti/SiO 2, Rh/Mn/SiO 2, Rh/Ti/Fe/Ir/SiO 2, Rh/Mn/MCM-41, Ni/S, Ni/Mo/S, Ni/Co/Mo/S and with the aforementioned substances of Mn and/or V combination in any.In addition, any in these catalyzer can (but needn't) comprise one or more alkaline promoters.
The composition of the catalyzer in reactor 105 and reactor 120 or reaction zone 110 and reaction zone 125 can be similar or or even identical.The association reaction district mentions that " the first catalyzer " and " the second catalyzer " is to mention different physical materials, needs not to be to mention that different catalyzer forms.In some embodiments, the catalyzer of some type is loaded in two reaction zones, but along with past of time, the nominal of these catalyzer forms and may depart from a little due to different exposure conditions.
In some versions, can comprise approximately 0% to about 50% methyl alcohol, approximately 10% to about 90% ethanol, approximately 0% to about 25% CO, approximately 0% to about 25% H from the product stream 130 of reactor 120 output 2With approximately 5% to about 25% CO 2And other gases.In some embodiments, product stream 130 also comprises one or more higher alcoholss, for example propyl alcohol or butanols.
Refer again to Fig. 1, in some versions, the unreacted synthetic gas in product stream 130 is separated to form incoming flow 135 and with further increase for example cycled through reactor 120, the yield of ethanol and/or other required products from product stream 130.Selectively or in addition, in some versions, the unreacted synthetic gas in product stream 130 is recycled by reactor 105 by it is joined in synthetic gas incoming flow 100.Yet if other materials that the unreacted synthetic gas in product stream 130 maybe can be poisoned the catalyst for methanol in reactor 105 by the compound of for example sulphur, sulphur, metal pollute, a kind of so rear method may be unaccommodated.
And, in some versions, methanol feed stream 140 is joined intermediate product stream 115 or with further increase for example is incorporated in addition in reactor 120 yield of ethanol and/or other required products.For example, the methyl alcohol in product stream 130 can be separated (not shown) from product stream 130 and also then be cycled through reactor 120.From the methyl alcohol in other sources also be directed in reactor 120 or as an alternative thing be introduced in reactor 120.
In some versions, one or more catalyzer in reactor 105, one or more catalyzer in reactor 120 or reactor 105 and reactor 120 one or more catalysts CO in both 2Be converted into methyl alcohol.CO during methanol can be present in synthetic gas incoming flow 100 by consumption thus in reactor 105, reactor 120 or two reactors 2Improve.Therefore, in some versions, with CO 2Join in synthetic gas incoming flow 100, perhaps control the production of synthetic gas incoming flow 100 and/or adjusting subsequently and have the CO of aequum with production 2Synthetic gas.In some versions, be used for CO 2The suitable catalyzer that is converted into methyl alcohol can comprise one or more in above-mentioned those catalyzer listed that use in reactor 105 and reactor 120.In some versions, by consuming CO 2The production that improves methyl alcohol can be by with methanol conversion being ethanol and/or by the H in the resulting synthetic air-flow that is introduced in reactor 120 2The favourable adjusting of/CO ratio, and cause the production of the ethanol of improvement.
With reference now to Fig. 2,, some selectable versions are different from above-mentioned those versions, are mainly to comprise the single reaction vessel 200 of the first reaction zone 205 and second reaction zone 810 rather than two reactors by use.Synthetic gas incoming flow 100 is incorporated in the first reaction zone 205, wherein one or more catalyzer are converted into methyl alcohol with at least a portion of synthetic gas incoming flow 100, at least a portion of comprising from the unreacted synthetic gas of incoming flow 100, methyl alcohol to be provided and in some versions, to comprise the intermediate product stream 115 of higher alcohols and/or other reaction product.At least a portion of intermediate product stream 115 is incorporated in second reaction zone 810, wherein one or more catalyzer will transform from least a portion of the synthetic gas of intermediate product stream 115 and/or from least a portion of the methyl alcohol of intermediate product stream 115, comprise ethanol and in some versions to provide, comprise methyl alcohol, higher alcohols, other reaction product and/or from the product stream 130 of the unreacted synthetic gas of intermediate product stream 115.
Reactor 200 can be the suitable catalyticreactor that comprises any type of two or more reaction zones.The operation of reactor 200 can be similar to the operation of above-mentioned reactor 105 and reactor 120.Particularly, in some versions, the catalyzer that uses in reaction zone 205 and reaction zone 810 and the operational condition of reaction zone are identical or similar with those catalyzer and operational condition in above-mentioned reaction zone 110 and reaction zone 120 respectively.In some versions, the composition of intermediate product stream 115 and product stream 130 is identical or similar with those compositions of the above-mentioned version of describing about Fig. 1.Synthetic gas in product stream 130 can be recycled by reaction zone 810 or be added in incoming flow 100.Can be with CO 2Join in synthetic gas incoming flow 100, perhaps can control the production of synthetic gas incoming flow 100 and/or adjusting subsequently has for the CO that improves the methanol production aequum with production 2Synthetic gas.The methanol feed stream (not shown) can be incorporated in reaction zone 810 in order to further for example increase the yield of ethanol and/or other required products.For example, this methanol feed stream can be separated from product stream 130.
Be similar to the version of two reactors, in some of the version of single reaction vessel, the H in intermediate product stream 115 2/ CO ratio can affect the yield of ethanol in reaction zone 810 and other products.In some versions, the H in intermediate product stream 115 2/ CO ratio is different from the H of incoming flow 100 2/ CO ratio, and H than incoming flow 100 is provided in reaction zone 810 2The ethanol yield that the ethanol yield that/CO ratio provides is high.In these versions, the viewpoint of the ethanol yield from reactor 120, methanol has for example improved the H that is fed into the synthetic gas in reaction zone 810 in reaction zone 205 2/ CO ratio.
With reference now to Fig. 3,, some selectable versions are different from described those versions about Fig. 1, this is because before in product stream 115 is incorporated into reactor 120, and at least a portion (some or substantially all) of the methyl alcohol in intermediate product stream 115 is transferred in methanol product stream 300.Methyl alcohol in product stream 300 can separate and purifying by ordinary method.Similarly as mentioned above, in some of these versions, the H in intermediate product stream 115 2/ CO ratio is different from the H of incoming flow 100 2/ CO ratio, and H than incoming flow 100 is provided in reactor 120 2The ethanol yield that the ethanol yield that/CO ratio provides is high.Therefore, in some of these versions, methanol can advantageously improve the alcohol production in reactor 120 in reactor 105.
In some versions, methyl alcohol in the first reactor by with high produced in yields and then be converted into ethanol in the second reactor.Example reference below in greater detail Fig. 4 describe.
With reference to figure 5, for example, in some versions, synthetic gas incoming flow 100 in the first reactor 105 with for example at least about 50%, preferably at least about 75% or even higher yield (CO is to the molar yield of methyl alcohol) be catalytically conveted to methyl alcohol.High like this methyl alcohol yield can be for example be promoted by some or substantially all in the non-methyl alcohol component in intermediate product stream 115 are separated into stream 500, and stream 500 is recycled by reactor 105.
The part that is not recycled (randomly) that is rich in methyl alcohol of intermediate product stream 115 is mixed with another kind of synthetic gas incoming flow 510, so that the incoming flow 515 that is introduced in reactor 120 to be provided.Be introduced at least a portion of methyl alcohol in reactor 120 and (randomly) synthetic gas by catalyzed conversion, comprise ethanol and in some versions to provide, comprise methyl alcohol, higher alcohols, other reaction product and/or from the product stream 130 of the unreacted synthetic gas of incoming flow 515.In some versions, the unreacted synthetic gas in product stream 130 is recycled by reactor 120 and/or is recycled by reactor 105 as incoming flow 135.The various components of product stream 130 can be separated and/or purifying as mentioned above.
In some versions, can regulate methyl alcohol in incoming flow 100 and the ratio of CO, for example in order to optimize the yield of the ethanol in reactor 120.In some embodiments, the molar ratio of the methyl alcohol/CO in reactor 120 approximately 0.5 arrives approximately between 2.0.In specific embodiment, the ratio of the methyl alcohol/CO in reactor 120 is approximately 1.0.
Any suitable catalyzer or the combination of catalyzer can be used in reactor 105.The suitable catalyzer that is used for reactor 105 can include but not limited to, the above-mentioned catalyst for methanol of listing.Similarly, any suitable catalyzer or the combination of catalyzer can be used in reactor 120.The suitable catalyzer that is used for reactor 120 can include but not limited to, the above-mentioned alcohol catalysis agent of listing.The composition of the catalyzer in reactor 105 and reactor 120 can be similar or even substantially the same.
In the version of any in the method for use the first reaction zone described herein and second reaction zone, can be incorporated in the first reaction zone and second reaction zone initially synthesizing air-flow.In some embodiments, synthetic gas is from external source.In some embodiments, synthetic gas from method described herein any (as, from the residual synthetic gas of the first reaction zone or second reaction zone).
In some embodiments of any in method described herein, will join from the synthetic gas in any source in the first reaction zone and/or second reaction zone.In some embodiments of any in method described herein, will join in second reaction zone from the methyl alcohol in any source.
Some embodiment has been utilized a plurality of physical reaction devices in one or two in reaction zone.For example, the firstth district can be comprised of two reactors, is then that single reaction vessel is as Second Region.Perhaps, in another example, the firstth district can be a reactor, and the back is two reactors in Second Region.Usually, any " district " or " reaction zone " can comprise the part of one, two, three or more physical reaction device.
In some embodiments of any in method described herein, be used for synthetic gas be converted into methyl alcohol, with synthetic gas and/or methanol conversion be ethanol or with the methyl alcohol homology turn to ethanol reaction conditions (as, temperature and pressure) with No. the 4th, 371,724, United States Patent (USP), the 4th, 424, No. 384, the 4th, 374, No. 285, the 4th, 409, No. 405, the 4th, 277, No. 634, the 4th, 253, No. 987, the 4th, 233, No. 466 and the 4th, those reaction conditionss of describing in any in 171, No. 461 are identical.
Fig. 4 has shown the example of a method, and wherein synthetic gas is catalytically conveted to methyl alcohol in the first reactor, and is converted into ethanol from the methyl alcohol of the first reactor and residual synthetic gas in the second reactor.With reference now to Fig. 4,, during in single two-stage, cold reciprocation compressor 405 is compressed to synthetic gas incoming flow 400 about 1500psig and it is supplied to synthetic gas preheater 410 at the about temperature of 135 °F.Preheater 410 is to use steam as the shell-and-tube exchanger in enthalpy source.
In this example relevant with Fig. 4, will deliver in reactor protection bed (reactor guard bed) 420,425 from the synthetic gas 415 of the heating of preheater 410.Protection bed 420,425 is built into permanent lead-lag and arranges (lead-lag arrangement), but tubulose, make any bed can establish bypass.Piping layout allows a bed in use, and another bed regenerating or activate.Regeneration starts by the hydrogen of mixing and the pipeline (not shown) of nitrogen.Protection bed 425,420 has been removed sulphur and the metal that for example can poison catalyst for methanol.In some embodiments, by adsorbing to remove one or more catalyzer poisons with copper, copper chromite, nickel, cobalt or molybdenum.These and other metals can be loaded in the high-temperature inorganic oxide material of high surface area, for example on aluminum oxide, silicon-dioxide, alumina/silica, clay or diatomite.A kind of exemplary material is the copper that is stated from aluminum oxide.In the future the exit gas 430 of self-insurance apron 420,425 is delivered in pure reactor by the about interchanger 435 under 350 °F, and uses the thick pure exit gas 470 from the second pure reactor 460 to be heated to approximately 480 °F during heat exchange.
Continuation is with reference to figure 4, approximately 1500psig and approximately the synthetic gas under 480 °F enter in the first alcohol synthesis reaction device 440, wherein experience catalyzed reaction in the tubular reactor of the supported catalyst of at least a portion of synthetic gas in reaction vessel.In some versions, the catalyzer in reactor 440 is the Cu/ZnO/ aluminium oxide catalyst.Expectation methyl alcohol is via reaction CO+2H 2→ CH 3OH forms.As before mentioning in this detailed description, in some versions, methyl alcohol can also pass through CO 2Hydrogenation form.
Product gas 450 leaves alcohol synthesis reaction device 440 with the about temperature of 500 °F, and enters in alcohol synthesis reaction device 460.In addition, with methyl alcohol stream 465 (as, from the isolated methanol loop stream of thick alcohol stream 470) mix with the product gas 450 that comes autoreactor 440, and also be introduced in reactor 460.The reaction that occurs in reactor 460 can comprise that ethanol forms.
Thick alcohol stream 470 leaves reactor 460 with the about temperature of 650 °F, and is cooled to the approximately temperature of 530 °F by interchanger 435 heat exchange in pure reactor.Recovery of heat subsequently and other cooling step (not shown)s are cooled to approximately 100 °F with thick alcohol stream 470.Ethanol, the methyl alcohol of thick alcohol stream 470, residual synthetic gas can be by separating and (randomly) purifying with method described herein or with the ordinary method (not shown) with other components.Can for example by being mixed to be recycled with synthetic gas incoming flow 400, it pass through reactor from flowing 470 synthetic gas that reclaim.
Except the industrial heat of routine (as, steam, from the heat of burner, used heat etc.) outside or replace conventional industrial heat (as, steam, from the heat of burner, used heat etc.), some versions can adopt microwave, radio frequency, laser and/or UV energy, to promote the production of ethanol.For example, microwave, radio frequency, laser and/or UV energy can be used for the CO with synthetic gas in some versions 2Be converted into CO and O 2, in order to more effectively be catalytically conveted to methyl alcohol and/or ethanol.In some embodiments, for the CO with synthetic gas 2Be converted into CO ordinary method (as, with promoting CO 2Be converted into the catalyst treatment synthetic gas of CO) for more effectively being catalytically conveted to methyl alcohol and/or ethanol.In some embodiments, catalyzer and radiation (as, with microwave, radio frequency, laser and/or UV energy emission) all be used for CO 2Be converted into CO.In specific embodiment, remove CO from synthetic gas 2, and radiation (as, with microwave, radio frequency, laser and/or UV energy emission) and/or catalyzer (as, thermocatalyst) be used for producing O by CO 2Remove O 2, and with CO join first and/or second reaction zone in.In some embodiments, radiation allows when there is no radiation for CO 2Be converted into standard temperature and low being used for CO of standard pressure of CO 2Be converted into temperature and/or the pressure of CO.In some versions, the CO in synthetic air-flow 100 2Can this mode randomly be transformed.
As another example, microwave, radio frequency, laser and/or UV energy can be used for promoting that syngas catalytic conversion is methyl alcohol and/or ethanol, and/or be used for promoting that at the various versions for the aforesaid method that synthetic gas is converted into ethanol synthetic gas and/or methanol oxidation are converted into ethanol.More generally, in some versions, microwave, radio frequency, laser and/or UV energy can be used for promoting that the syngas catalytic conversion in any source is methyl alcohol and/or ethanol, and/or be used for promoting the synthetic gas in any source and/or methanol oxidation to be converted into ethanol.
In some embodiments, microwave, radio frequency, laser and/or UV energy are used for synthetic gas and/or first catalyzer of radiation the first reaction zone, to improve synthetic gas to the transformation efficiency of methyl alcohol.In some embodiments, radiation has increased molecular vibration, has increased energy density or has otherwise activated synthetic gas and/or the first catalyzer.Microwave, radio frequency, laser and/or UV energy for example can allow reactor to operate under than the low temperature and pressure of other modes in synthetic gas to this purposes in methanol reactor.
In some versions, microwave, radio frequency, laser and/or UV energy are used for synthetic gas, methyl alcohol and/or second catalyzer of radiation second reaction zone.In some embodiments, radiation has increased molecular vibration, has increased energy density or has otherwise activated synthetic gas, methyl alcohol and/or the second catalyzer.For example, by by methyl alcohol preferential absorption microwave, radio frequency, laser and/or UV energy, allow to obtain high energy density in methanol reactant, methyl alcohol can occur to the catalyzed conversion of the improvement of ethanol.For example microwave is with than adding the fast speed heating methanol of hot ethanol, and being conducive to thus methanol conversion is ethanol.Microwave, radio frequency, laser and/or UV energy for example can allow reactor to operate under than the low temperature and pressure of other modes in methyl alcohol to this purposes in the ethanol synthesis device.
In some embodiments, described method comprise with synthetic gas be incorporated into the reaction zone that comprises at least a catalyzer (as, reactor) in and with energy (as, microwave, radio frequency, laser and/or UV energy) synthetic gas and/or catalyzer in the radioreaction district.At least a portion of synthetic gas can be converted into ethanol.Described method can also methanol or other alcohol.Suitable catalyzer can include but not limited to, any in catalyzer described herein.In some embodiments, catalyzer is for synthetic gas being converted into the conventional catalyst of ethanol at a reaction zone or a reactor.In some embodiments, catalyzer is conducive in the situation that there is no radiation through the formation of methanol ethanol, and radiation has improved the selectivity that forms ethanol.For example, radiation can be than adding the fast speed heating methanol of hot ethanol, and being conducive to thus methanol conversion is ethanol.In some embodiments, catalyzer is conducive in the situation that do not have radiation to form methyl alcohol through ethanol, and the radiation methyl alcohol that makes Catalyst Production to the ratio of ethanol lower than making the methyl alcohol of Catalyst Production to the ratio of ethanol in the situation that there is no radiation.For example, radiation can make the ethanol of catalyzer production now more than methyl alcohol.
In other embodiments, described method comprise synthetic gas and/or methyl alcohol are incorporated in the reaction zone that comprises at least a catalyzer and with energy (as, microwave, radio frequency, laser and/or UV energy) synthetic gas, methyl alcohol and/or catalyzer in the radioreaction district.At least a portion of synthetic gas and/or methyl alcohol is converted into ethanol.Described method can also be produced other alcohol.In specific embodiment, synthetic gas and methyl alcohol all are introduced in reaction zone.In some embodiments, synthetic gas or methyl alcohol are introduced in reaction zone.In some embodiments, come methanol or obtain methyl alcohol from any other source with any in method described herein, and the methyl alcohol that will not contain synthetic gas is incorporated in reaction zone.Suitable catalyzer can include but not limited to, any in catalyzer described herein.
In some embodiments, in the following manner from product stream 130 or thick alcohol stream 470 purifying ethanols: at first desciccate stream 130 or thick alcohol flow 470 with the generation intermediate product, and then distill intermediate product to produce the ethanol product of purifying.In some embodiments, product stream 130 or thick alcohol stream 470 comprise ethanol, methyl alcohol, propyl alcohol, fourth alcohol and water.In some embodiments, product stream 130 or thick alcohol stream 470 comprise one or more in following alcohol: 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, the trimethyl carbinol, amylalcohol, hexanol, enanthol and octanol and/or higher alcohols.In some embodiments, product stream 130 or thick alcohol stream 470 comprise one or more aldehyde, ketone and/or organic acid (as formaldehyde, acetaldehyde, acetic acid and analogue).
In specific embodiment, the amount of ethanol product stream 130 by weight or thick alcohol stream 470 approximately 25% to approximately between 95%, for example by weight approximately between 30% to 50% or by weight approximately 50% to approximately between 90%.In specific embodiment, the amount of methyl alcohol product stream 130 by weight or thick alcohol stream 470 approximately 1% to approximately between 50%, for example by weight approximately between 5% to 25% or by weight approximately 25% to approximately between 55%.In specific embodiment, the amount of water product stream 130 by weight or thick alcohol stream 470 approximately 1% to approximately between 50%, for example by weight approximately between 1% to 10% or by weight approximately 10% to approximately between 20%.In specific embodiment, the amount of propyl alcohol product stream 130 by weight or thick alcohol stream 470 approximately 0.5% to approximately between 10%, for example by weight approximately between 1% to 2% or by weight approximately 2% to approximately between 8%.In specific embodiment, butanols product stream 130 by weight or thick alcohol stream 470 approximately 0.2% to approximately between 0.5%, for example by weight approximately between 0.5% to 2% or by weight approximately 2% to approximately between 5%.
In specific embodiment, the total amount of ketone and aldehyde product stream 130 by weight or thick alcohol stream 470 approximately 0.1% to approximately between 10%, for example approximately 0.5% to approximately between 2%.In specific embodiment, the organic acid total amount product stream 130 by weight or thick alcohol stream 470 approximately 0.1% to approximately between 10%, for example approximately 0.5% to approximately between 2%.In specific embodiment, C 5And the total amount of higher alcohols product stream 130 by weight or thick alcohol stream 470 approximately 0.1% to approximately between 5%, for example approximately 0.5% to approximately between 2%.
In specific embodiment, implementing drying before distillation rather than after distillation.Drying step can be reduced by at least 75% with the amount of the water in product stream 130 or thick alcohol stream 470, and preferably at least 90%, more preferably at least 95% and most preferably at least about 99%.In specific embodiment, the amount of water is less than or equal to approximately 1% or still less of intermediate product by weight.Drying can also be called as " dehydration ", and " dehydration " refers to remove water rather than remove anhydrate (for example during alkene forms) at molecular level at this paper from solution.
In some embodiments, drying step comprise allow product stream 130 or thick alcohol stream 470 by such as the film of zeolite membrane or by one or more molecular sieves to produce intermediate product.In some embodiments, molecular sieve has less than the about effective pore radius of 5 dusts.In certain embodiments, molecular sieve has the approximately effective pore radius of 3 dusts.
In other embodiments, drying step comprises that allowing product stream 130 or thick alcohol flow 470 passes through siccative.Known many kinds of siccative.For example, siccative can be selected from SiO 2, CaO, CaCO 3, CaCl 2, CuSO 4Or CaSO 4
Conventional distillating method well known in the art can be used for the distillation intermediate product.Can use the distillation tower of any amount, this depends on desired overall separation.In some embodiments, ethanol purified product by weight approximately 95% to approximately between 99.9%.As will be appreciated, the ethanol product of purifying can be manufactured to the specification of the ASTM D4806-07a that satisfies alcohol fuel or the specification of certain other fuel-grade.
The ethanol product of purifying can be used for providing power to drive transportation means for oil engine.In some embodiments, the ethanol product of purifying can with at least a other hydrocarbon or such as the hydrocarbons of gasoline combination (blend) to form the liquid fuel blend.
In this detailed description, with reference to a plurality of embodiments of the present invention and about how to understand and put into practice nonrestrictive example of the present invention.Can use other embodiments that all Characteristics and advantages in this paper are not provided, and without departing from the spirit and scope of the present invention.The present invention is in conjunction with normal experiment and the optimization of method and system as herein described.This type of modifications and variations form is considered to be in the scope of the present invention that is defined by claim.
All publications, patent and the patent application of quoting in this specification sheets are incorporated this paper into its integral body by reference, as each publication, patent or patent application particularly and individually this paper proposes.
If aforesaid method and step represent some event of occurring in sequence with certain, those of ordinary skill in the art will recognize so, and the sequence of some step can be modified, and these changes are according to version of the present invention.In addition, when possibility, some step in each step can be implemented by parallel mode simultaneously, and sequentially implements.
Therefore, just have multiple version of the present invention, the expectation this patent also will cover those versions, and described version is at present disclosure or in the appended claims in the scope of spirit of the Equivalent of the present invention of discovery.The present invention should only be limited by desired right.

Claims (37)

1. one or more pure methods of purifying, the group that described alcohol selects free methyl alcohol, ethanol, propyl alcohol and butanols to form said method comprising the steps of: (a) drying comprises the original mixture of methyl alcohol, ethanol, propyl alcohol, fourth alcohol and water to produce intermediate product; And then (b) distills described intermediate product to produce the alcohol of one or more purifying.
2. method according to claim 1, the amount of the ethanol in wherein said original mixture is by weight between 25% and 95%.
3. method according to claim 1, the amount of the methyl alcohol in wherein said original mixture is by weight between 0.1% and 50%.
4. method according to claim 1, the amount of the water in wherein said original mixture is by weight between 1% and 50%.
5. method according to claim 1, the amount of the water in wherein said intermediate product is by weight less than 5%.
6. method according to claim 5, the described amount of the described water in wherein said intermediate product is by weight less than 0.5%.
7. method according to claim 1, wherein said step (a) is removed the water that is present at least 75% in described original mixture.
8. method according to claim 7, wherein said step (a) is removed the water that is present at least 95% in described original mixture.
9. method according to claim 1, wherein said step (a) comprises makes described original mixture pass through film.
10. method according to claim 9, wherein said film is zeolite membrane.
11. comprising, method according to claim 1, wherein said step (a) make described original mixture pass through siccative.
12. method according to claim 11, wherein said siccative selects free SiO 2, CaO, CaCO 3, CaCl 2, CuSO 4And CaSO 4The group that forms.
13. comprising, method according to claim 1, wherein said step (a) make described original mixture pass through molecular sieve.
14. method according to claim 13, wherein said molecular sieve has the effective pore radius less than 5 dusts.
15. method according to claim 14, wherein said molecular sieve has the effective pore radius of 3 dusts.
16. method according to claim 1, a kind of in the alcohol of wherein said purifying is ethanol.
17. method according to claim 1, a kind of in the alcohol of wherein said purifying is the 1-propyl alcohol.
18. method according to claim 1, a kind of in the alcohol of wherein said purifying is n-butyl alcohol.
19. method according to claim 1, wherein said distillation produces the methanol product of purifying and the ethanol product of purifying.
20. method according to claim 1, wherein said distillation produces methanol product, the ethanol product of purifying and the 1-propyl alcohol product of purifying of purifying.
21. method according to claim 16, the alcohol concn of wherein said ethanol is by weight between 95% and 99.9%.
22. method according to claim 16, wherein said ethanol satisfy the specification of the ASTM D4806-07a of alcohol fuel.
23. method according to claim 1, it comprises also that at least in part the alcohol with described one or more purifying provides power for oil engine.
24. method according to claim 1, it also comprises the alcohol of described one or more purifying is mixed with at least a other hydrocarbon, produces thus the liquid fuel blend.
25. method according to claim 24, it also comprises at least in part provides power with described liquid fuel blend for oil engine.
26. the group that a method of producing the alcohol of purifying, the alcohol of described purifying select free methyl alcohol, ethanol, propyl alcohol and butanols to form said method comprising the steps of:
(a) make the carbon-containing feeding devolatilization to form gas phase and solid phase in the devolatilization unit;
(b) make described gas phase and described solid phase pass through the reaction vessel of heating to form synthetic gas;
(c) described synthetic gas is converted into the mixture that comprises methyl alcohol, ethanol, propyl alcohol, fourth alcohol and water;
(d) dry described mixture is to produce intermediate product; And
(e) the described intermediate product of distillation is to produce the alcohol of purifying.
27. method according to claim 26, the amount of the water in wherein said intermediate product is by weight less than 5%.
28. method according to claim 26, the amount of the described water in wherein said intermediate product is by weight less than 0.5%.
29. method according to claim 26, at least 95% of the amount of the water in the described mixture of wherein said step (d) minimizing.
30. comprising, method according to claim 26, wherein said step (d) make described mixture pass through zeolite membrane.
31. comprising, method according to claim 26, wherein said step (d) make described mixture pass through siccative.
32. comprising, method according to claim 26, wherein said step (d) make described mixture pass through molecular sieve.
33. the group that the device for the production of the alcohol of purifying, the alcohol of described purifying select free methyl alcohol, ethanol, propyl alcohol and butanols to form, described device comprises:
(a) be used for making the carbon-containing feeding devolatilization to form the equipment of gas phase and solid phase in the devolatilization unit;
(b) be used for making described gas phase and described solid phase to pass through the reaction vessel of heating with the equipment of formation synthetic gas;
(c) be used for described synthetic gas is converted into the equipment of the mixture that comprises ethanol, methyl alcohol, propyl alcohol, fourth alcohol and water;
(d) be used for dry described mixture to produce the equipment of intermediate product; And
(e) be used for distilling described intermediate product with the equipment of the alcohol of production purifying,
Wherein said device is configured to be used for described drying before described distillation.
34. device according to claim 33, wherein (d) comprises zeolite membrane.
35. device according to claim 33, wherein (d) comprises siccative.
36. device according to claim 33, wherein (d) comprises the molecular sieve that has less than the effective pore radius of 5 dusts.
37. device according to claim 36, wherein said molecular sieve has the effective pore radius of 3 dusts.
CN2012104742355A 2007-07-09 2008-07-02 Methods and apparatus for producing alcohols from syngas Pending CN103121922A (en)

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US12/166,203 US20090018371A1 (en) 2007-07-09 2008-07-01 Methods and apparatus for producing alcohols from syngas
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